Method for the production of absorbent polymer particles by polymerizing drops of a monomer solution

ABSTRACT

A process for preparing water-absorbing polymer beads by polymerizing droplets comprising at least one monomer in a gas phase surrounding the droplets, the droplets being obtained by enveloping a first monomer solution with a second monomer solution and polymerizing the second monomer solution and polymerizing to give a more highly crosslinked polymer than the first monomer solution.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional of U.S. patent application Ser. No. 12/438,226,filed Feb. 20, 2009, now U.S. Pat. No. 8,529,805, which the U.S.national phase of International Application No. PCT/EP2007/060416, filedOct. 2, 2007, which claims the benefit of European Patent ApplicationNo. 06121838.4, filed Oct. 5, 2006.

The present invention relates to a process for preparing water-absorbingpolymer beads by polymerizing droplets comprising at least one monomerin a gas phase surrounding the droplets, the droplets being obtained bysurrounding a first monomer solution with a second monomer solution andpolymerizing the second monomer solution to give a more highlycrosslinked polymer than the first monomer solution.

The preparation of water-absorbing polymer beads is described in themonograph “Modern Superabsorbent Polymer Technology”, F. L. Buchholz andA. T. Graham, Wiley-VCH, 1998, pages 71 to 103.

Being products which absorb aqueous solutions, water-absorbing polymersare used to produce diapers, tampons, sanitary napkins and other hygienearticles, but also as water-retaining agents in market gardening.

Spray polymerization allows the process steps of polymerization anddrying to be combined. In addition, the bead size can be set withincertain limits by virtue of suitable process control.

The preparation of water-absorbing polymer beads by polymerization ofdroplets of a monomer solution is described, for example, in EP 348 180A1. JP 05/132503 A. WO 96/40427 A1, U.S. Pat. No. 5,269,980, DE 103 14466 A1, DE 103 40 253 A1 and DE 10 2004 024 437 A1, WO 2006/077054 A1,and also the prior German application 102006001596.7 and the prior PCTapplication PCT/EP2006/062252.

JP 05/132503 A discloses a spray polymerization process by redoxpolymerization, wherein the components of the redox initiator are notmixed until beyond the nozzle.

WO 2006/077054 A1 describes a process in which use of surface-activecrosslinkers generates a crosslinker gradient.

The prior PCT application PCT/EP2006/062252 describes a process whereina concentration gradient is obtained in the droplets by means of atwo-substance nozzle.

DE 10 2004 042 946 A1, DE 10 2004 042 948 A1 and DE 10 2004 042 955A1.and also the prior German application 102005019398.6, describe thepreparation of thickeners by spray polymerization.

It was an object of the present invention to provide an improved processfor preparing water-absorbing polymer beads by polymerizing droplets ofa monomer solution in a gas phase surrounding the droplets.

The object is achieved by a process for preparing water-absorbingpolymer beads by polymerizing droplets comprising

-   a) at least one ethylenically unsaturated monomer,-   b) at least one crosslinker,-   c) at least one initiator,-   d) water,    in a gas phase surrounding the droplets, the droplets being obtained    by enveloping a first monomer solution with a second monomer    solution, wherein the second monomer solution polymerizes to give a    more highly crosslinked polymer than the first monomer solution.

By virtue of the second monomer solution polymerizing to give a morehighly crosslinked polymer, water-absorbing polymer beads with acrosslinking gradient are obtained in one step. The higher crosslinkingcan be achieved, for example, by virtue of a higher crosslinkerconcentration and/or a more effective crosslinker in the second monomersolution.

The molar crosslinker concentration in the second monomer solution istypically at least 10%, preferably at least 20%, preferentially at least50%, more preferebk/at least 100%, most preferably at least 200%, higherthan in the first monomer so(ution.

The first monomer solution comprises preferably at least 0.2% by weight,preferentially at least 0.4% by weight, more preferably at least 0.6% byweight, most preferably at least 0.8% by weight, of crosslinker b),based in each case on monomer a).

The second monomer solution comprises preferably at least 0.6% byweight, preferentially at least 0.8% by weight, more preferably at least1.5% by weight, most preferably at least 3.0% by weight, of crosslinkerb), based in each case on monomer a).

In a preferred embodiment of the present invention, the second monomersolution is metered in through an annular gap surrounding the feed ofthe first monomer solution. The annular gap has a gap width ofpreferably from 25 μm to 250 μm, more preferably from 50 to 200 μm, mostpreferably from 100 to 150 μm.

The droplets obtained have a mean diameter of preferably at least 200μm, more preferably of at least 250 μm, most preferably of at least 300μm, the droplet diameter being determinable by light scattering.

The droplets are preferably monodisperse; more preferably, less than 10%by weight of the droplets have a diameter which deviates by more than50% from the mean diameter.

The water-absorbing polymer beads obtainable by the process according tothe invention have a permeability (SFC) of typically at least 10×10⁻⁷cm³s/g, preferably at least 30×10⁻⁷ cm³s/g, preferentially at least50×10⁻⁷ cm³s/g, more preferably at least 70×10⁻⁷ cm³s/g, most preferablyat least 90×10⁻⁷ cm³s/g. The permeability (SFC) of the water-absorbingpolymer beads is typically less than 250×10⁻⁷ cm³s/g.

The water-absorbing polymer beads obtainable by the process according tothe invention have an absorbency under a load of 4.83 kPa (AUL0.7 psi)of typically at least 15 g/g, preferably of at least 20 g/g,preferentially at least 25 g/g, more preferably of at least 27 g/g, mostpreferably of at least 29 g/g. The absorbency under a load of 4.83 kPa(AUL0.7 psi) of the water-absorbing polymer beads is typically less than50 g/g.

The water-absorbing polymer beads obtainable by the process according tothe invention have a centrifuge retention capacity (CRC) of typically atleast 20 g/g, preferably at least 25 g/g, preferentially at least 30g/g, more preferably at least 32 g/g, most preferably at least 34 g/g.The centrifuge retention capacity (CRC) of the water-absorbing polymerbeads is typically less than 50 g/g.

The water-absorbing polymer beads obtainable by the process according tothe invention have a content of extractables of typically less than 15%by weight, preferably less than 10% by weight, preferentially less than5% by weight, more preferably less than 4% by weight, most preferablyless than 3% by weight.

The process according to the invention enables the preparation ofwater-absorbing polymer beads with very uniform crosslinking density atthe bead surface.

In the measurement of the modulus of elasticity of the outer beadsurface, typically less than 50%, preferably less than 40%,preferentially less than 30%, more preferably less than 25%, mostpreferably less than 20%, have a modulus of elasticity of less than 60%of the mean modulus of elasticity.

The water-absorbing polymer beads obtainable by the process according tothe invention have a mean modulus of elasticity of the outer beadsurface of typically at least 50 kPa, preferably at least 90 kPa,preferentially at least 120 kPa, more preferably at least 150 kPa, mostpreferably at least 180 kPa. The mean modulus of elasticity of the outerbead surface of the water-absorbing polymer beads is typically less than500 kPa.

The mean diameter of the water-absorbing polymer beads obtainable by theprocess according to the invention is preferably at least 200 μm, morepreferably from 250 to 600 μm, very particularly from 300 to 500 μm, thebead diameter being determinable by light scattering and meaning thevolume-average mean diameter. 90% of the polymer beads have a diameterof preferably from 100 to 800 μm, more preferably from 150 to 700 μm,most preferably from 200 to 600 μm.

The monomers a) are preferably water-soluble, i.e. the solubility inwater at 23° C. is typically at least 1 g/100 g of water, preferably atleast 5 g/100 g of water, more preferably at least 25 g/100 g of water,most preferably at least 50 g/100 g of water, and preferably have atleast one acid group each.

Suitable monomers a) are, for example, ethylenically unsaturatedcarboxylic acids such as acrylic acid, methacrylic acid, maleic acid,fumaric acid and itaconic acid. Particularly preferred monomers areacrylic acid and methacrylic acid. Very particular preference is givento acrylic acid.

The preferred monomers a) have at least one acid group, the acid groupspreferably being at least partly neutralized.

The proportion of acrylic acid and/or salts thereof in the total amountof monomers a) is preferably at least 50 mol %, more preferably at least90 mol %, most preferably at least 95 mol %.

The acid groups of the monomers a) are typically partly neutralized,preferably to an extent of from 25 to 85 mol %, preferentially to anextent of from 50 to 80 mol %, more preferably from 60 to 75 mol %, forwhich the customary neutralizing agents can be used, preferably alkalimetal hydroxides, alkali metal oxides, alkali metal carbonates or alkalimetal hydrogencarbonates, and mixtures thereof. Instead of alkali metalsalts, it is also possible to use ammonium salts. Sodium and potassiumare particularly preferred as alkali metals, but very particularpreference is given to sodium hydroxide, sodium carbonate or sodiumhydrogencarbonate, and mixtures thereof. Typically, the neutralizationis achieved by mixing in the neutralizing agent as an aqueous solution,as a melt or preferably also as a solid. For example, sodium hydroxidewith a water content significantly below 50% by weight may be present asa waxy material having a melting point above 23° C. In this case,metered addition as piece material or melt at elevated temperature ispossible.

The monomers a), especially acrylic acid, comprise preferably up to0.025% by weight of a hydroquinone monoether. Preferred hydroquinonemonoethers are hydroquinone monomethyl ether (MEHQ) and/or tocopherols.

Tocopherol is understood to mean compounds of the following formula

where R¹ is hydrogen or methyl, R² is hydrogen or methyl, R³ is hydrogenor methyl, and R⁴ is hydrogen or an acyl radical having from 1 to 20carbon atoms.

Preferred radicals for R⁴ are acetyl, ascorbyl, succinyl, nicotinyl andother physiologically compatible carboxylic acids. The carboxylic acidsmay be mono-, di- or tricarboxylic acids.

Preference is given to alpha-tocopherol where R¹=R²=R³=methyl, inparticular racemic alpha-tocopherol. R¹ is more preferably hydrogen oracetyl. RRR-alpha-tocopherol is especially preferred.

The monomer solution comprises preferably at most 130 ppm by weight,more preferably at most 70 ppm by weight, preferably at least 10 ppm byweight, more preferably at least 30 ppm by weight, in particular around50 ppm by weight, of hydroquinone monoether, based in each case onacrylic acid, acrylic acid salts also being considered as acrylic acid.For example, the monomer solution can be prepared by using acrylic acidhaving an appropriate content of hydroquinone monoether.

Crosslinkers b) are compounds having at least two free-radicallypolymerizable groups which can be polymerized by a free-radicalmechanism into the polymer network. Suitable crosslinkers b) are, forexample, ethylene glycol dinnethacrylate, diethylene glycol diacrylate,allyl methacrylate, trimethylolpropane triacrylate, triallylamine,tetraallyloxyethane, as described in EP 530 438 A1. di- andtriacrylates, as described in EP 547 847 A1, EP 559 476 A1, EP 632 068A1, WO 93/21237 A1, WO 2003/104299 A1, WO 2003/104300 A1, WO 2003/104301A1 and in DE 103 31 450 A1, mixed acrylates which, as well as acrylategroups, comprise further ethylenically unsaturated groups, as describedin DE 103 31 456 A1 and DE 103 55 401 A1, or crosslinker mixtures, asdescribed, for example, in DE 195 43 368 A1, DE 196 46 484 A1, WO90/15830 A1 and WO 2002/32962 A2.

Suitable crosslinkers b) are in particular N,N′-methylenebisacrylamideand N,N′-methylenebismethacrylamide, esters of unsaturated mono- orpolycarboxylic acids of polyols, such as diacrylate or triacrylate, forexample butanediol diacrylate, butanediol dimethacrylate, ethyleneglycol diacrylate or ethylene glycol dimethacrylate, and alsotrimethylolpropane triacrylate and allyl compounds such asallyl(meth)acrylate, triallyl cyanurate, diallyl maleate, polyallylesters, tetraallyloxyethane, triallylamine, tetraallylethylenediannine,allyl esters of phosphoric acid and vinylphosphonic acid derivatives, asdescribed, for example, in EP 343 427 A2. Further suitable crosslinkersb) are pentaerythritol diallyl ether, pentaerythritol triallyl ether andpentaerythritol tetraallyl ether, polyethylene glycol diallyl ether,ethylene glycol diallyl ether, glycerol diallyl ether and glyceroltriallyl ether, polyallyl ethers based on sorbitol, and ethoxylatedvariants thereof. In the process according to the invention, it ispossible to use di(meth)acrylates of polyethylene glycols, thepolyethylene glycol used having a molecular weight between 300 and 1000.

However, particularly advantageous crosslinkers b) are di- andtriacrylates of 3- to 20-tuply ethoxylated glycerol, of 3- to 20-tuplyethoxylated trimethylolpropane, of 3- to 20-tuply ethoxylatedtrimethylolethane, in particular di- and triacrylates of 2- to 6-tuplyethoxylated glycerol or of 2- to 6-tuply ethoxylated trimethylolpropane,of 3-tuply propoxylated glycerol or of 3-tuply propoxylatedtrimethylolpropane, and also of 3-tuply mixed ethoxylated orpropoxylated glycerol or of 3-tuply mixed ethoxylated or propoxylatedtrimethylolpropane, of 15-tuply ethoxylated glycerol or of 15-tuplyethoxylated trimethylolpropane, and also of 40-tuply ethoxylatedglycerol, of 40-tuply ethoxylated trimethylolethane or of 40-tuplyethoxylated trimethylolpropane.

Very particularly preferred crosslinkers b) are the polyethoxylatedand/or -propoxylated glycerols which have been esterified with acrylicacid or methacrylic acid to give di- or triacrylates, as described, forexample in WO 2003/104301 A1. Di- and/or triacrylates of 3- to 10-tuplyethoxylated glycerol are particularly advantageous.

Very particular preference is given to di- or triacrylates of 1- to5-tuply ethoxylated and/or propoxylated glycerol. Most preferred are thetriacrylates of 3- to 5-tuply ethoxylated and/or propoxylated glycerol.

The initiators c) used may be all compounds which disintegrate into freeradicals under the polymerization conditions, for example peroxides,hydroperoxides, hydrogen peroxide, persulfates, azo compounds and redoxinitiators. Preference is given to the use of water-soluble initiators.In some cases, it is advantageous to use mixtures of various initiators,for example mixtures of hydrogen peroxide and sodium or potassiumperoxodisulfate. Mixtures of hydrogen peroxide and sodiumperoxodisulfate can be used in any proportion.

Particularly preferred initiators c) are azo initiators such as2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride and2,2′-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, andphotoinitiators such as 2-hydroxy-2-methylpropiophenone and1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, redoxinitiators such as sodium persulfate/hydroxymethylsulfinic acid,ammonium peroxodisulfate/hydroxy-methylsulfinic acid, hydrogenperoxide/hydroxymethylsulfinic acid, sodium persulfate/ascorbic acid,ammonium peroxodisulfate/ascorbic acid and hydrogen peroxide/ascorbicacid, photoinitiators such as1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, andmixtures thereof.

The initiators are used in customary amounts, for example in amounts offrom 0.001 to 5% by weight, preferably from 0.01 to 1% by weight, basedon the monomers a).

For optimal action, the preferred polymerization inhibitors requiredissolved oxygen. Therefore, the monomer solution can be freed ofdissolved oxygen before the polymerization by inertization, i.e. flowingthrough with an inert gas, preferably nitrogen. The oxygen content ofthe monomer solution is preferably lowered before the polymerization toless than 1 ppm by weight, more preferably to less than 0.5 ppm byweight.

The polymerization inhibitors can also be removed by absorption, forexample on activated carbon.

The solids content of the monomer solution is preferably at least 35% byweight, preferably at least 38% by weight, more preferably at least 40%by weight, most preferably at least 42% by weight. The solids content isthe sum of all constituents which are involatile after thepolymerization. These are monomer a), crosslinker b) and initiator c).

The monomer solution is dropletized for polymerization in the gas phase.The oxygen content of the gas phase is preferably from 0.001 to 0.15% byvolume, more preferably from 0.002 to 0.1% by volume, most preferablyfrom 0.005 to 0.05% by volume.

As well as oxygen, the gas phase preferably comprises only inert gases,i.e. gases which, under reaction conditions, do not intervene in thepolymerization, for example nitrogen and/or steam.

The dropletization involves metering a monomer solution into the gasphase to form droplets. The dropletization of the monomer solution canbe carried out, for example, by means of a dropletizer plate.

A dropletizer plate is a plate having at least one bore, the liquidentering the bore from the top. The dropletizer plate or the liquid canbe oscillated, which generates a chain of ideally monodisperse dropletsat each bore on the underside of the dropletizer plate. In a preferredembodiment, the dropletizer plate is not agitated.

The number and size of the bores are selected according to the desiredcapacity and droplet size. The droplet diameter is typically 1.9 timesthe diameter of the bore. What is important here is that the liquid tobe dropletized does not pass through the bore too rapidly and thepressure drop over the bore is not too great. Otherwise, the liquid isnot dropletized, but rather the liquid jet is broken up (sprayed) owingto the high kinetic energy. The dropletizer is operated in the flowrange of laminar jet decomposition, i.e. the Reynolds number based onthe throughput per bore and the bore diameter is preferably less than2000, preferentially less than 1000, more preferably less than 500 andmost preferably less than 100. The pressure drop through the bore ispreferably less than 2.5 bar, more preferably less than 1.5 bar and mostpreferably less than 1 bar.

The dropletizer plate has typically at least one bore, preferably atleast 10, more preferably at least 50 and typically up to 10 000 bores,preferably up to 5000, more preferably up to 1000 bores, the borestypically being distributed uniformly over the dropletizer plate,preferably in so-called triangular pitch, i.e. three bores in each caseform the corners of an equilateral triangle. The diameter of the boresis adjusted to the desired droplet size.

However, the dropletization can also be carried out by means ofpneumatic drawing dies, rotation, cutting of a jet or rapidly actuablemicrovalve dies.

In a pneumatic drawing die, a liquid jet together with a gas stream isaccelerated through a diaphragm. The gas rate can be used to influencethe diameter of the liquid jet and hence the droplet diameter.

In the case of dropletization by rotation, the liquid passes through theorifices of a rotating disk. As a result of the centrifugal force actingon the liquid, droplets of defined size are torn off. Preferredapparatus for rotary dropletization are described, for example, in DE 4308 842 A1.

The emerging liquid jet can also be cut into defined segments by meansof a rotating blade. Each segment then forms a droplet.

In the case of use of microvalve dies, droplets with defined liquidvolume are generated directly.

The gas phase preferably flows as carrier gas through the reactionchamber. The carrier gas can be conducted through the reaction chamberin cocurrent or in countercurrent to the free-falling droplets of themonomer solution, preferably in cocurrent. After one pass, the carriergas is preferably recycled at least partly, preferably to an extent ofat least 50%, more preferably to an extent of at least 75%, into thereaction chamber as cycle gas. Typically, a portion of the carrier gasis discharged after each pass, preferably up to 10%, more preferably upto 3% and most preferably up to 1%.

The polymerization is preferably carried out in a laminar gas flow. Alaminar gas flow is a gas flow in which the individual layers of theflow do not mix but rather move in parallel. A measure of the flowconditions is the Reynolds number (Re). Below a critical Reynolds number(Re_(crit)) of 2300, the gas flow is laminar. The Reynolds number of thelaminar gas flow is preferably less than 2000, more preferably less than1500 and most preferably less than 1000. The lower limiting case of thelaminar inert gas flow is a standing inert gas atmosphere (Re=0), i.e.inert gas is not fed in continuously.

The gas velocity is preferably adjusted such that the flow in thereactor is directed, for example no convection currents opposed to thegeneral flow direction are present, and is, for example, from 0.01 to 5m/s, preferably from 0.02 to 4 m/s, more preferably from 0.05 to 3 m/s,most preferably from 0.1 to 2 m/s.

The carrier gas is appropriately preheated to the reaction temperatureupstream of the reactor.

The reaction temperature in the thermally induced polymerization ispreferably from 70 to 250° C., more preferably from 100 to 220° C. andmost preferably from 120 to 200° C.

The reaction can be carried out under elevated pressure or under reducedpressure; preference is given to a reduced pressure of up to 100 mbarrelative to ambient pressure.

The reaction offgas, i.e. the carrier gas leaving the reaction chamber,may, for example, be cooled in a heat exchanger. This condenses waterand unconverted monomer a). The reaction offgas can then be reheated atleast partly and recycled into the reactor as cycle gas. A portion ofthe reaction offgas can be discharged and replaced by fresh carrier gas,in which case water and unconverted monomers a) present in the reactionoffgas can be removed and recycled.

Particular preference is given to a thermally integrated system, i.e. aportion of the waste heat in the cooling of the offgas is used to heatthe cycle gas.

The reactors can be trace-heated. In this case, the trace heating isadjusted such that the wall temperature is at least 5° C. above theinternal reactor temperature and condensation on the reactor walls isreliably prevented.

The reaction product can be withdrawn from the reactor in a customarymanner, preferably at the bottom by means of a conveying screw, and, ifappropriate, dried down to the desired residual moisture content and tothe desired residual monomer content.

The polymer beads can subsequently be postcrosslinked for furtherimprovement of the properties.

Postcrosslinkers are compounds which comprise at least two groups whichcan form covalent bonds with the carboxylate groups of the hydrogel.Suitable compounds are, for example, alkoxysilyl compounds,polyaziridines, polyamines, polyamidoamines, di- or polyepoxides, asdescribed in EP 83 022 A2, EP 543 303 A1 and EP 937 736 A2, di- orpolyfunctional alcohols as described in DE 33 14 019 A1, DE 35 23 617 A1and EP 450 922 A2, or β-hydroxyalkylamides, as described in DE 102 04938 A1 and U.S. Pat. No. 6,239,230.

In addition, DE 40 20 780 C1 describes cyclic carbonates, DE 198 07 502A1 describes 2-oxazolidone and its derivatives such as2-hydroxyethyl-2-oxazolidone, DE 198 07 992 C1 describes bis- andpoly-2-oxazolidinones, DE 198 54 573 A1 describes2-oxotetrahydro-1,3-oxazine and its derivatives, DE 198 54 574 A1describes N-acyl-2-oxazolidones, DE 102 04 937 A1 describes cyclicureas. DE 103 34 584 A1 describes bicyclic amide acetals. EP 1 199 327A2 describes oxetanes and cyclic ureas, and WO 2003/31482 A1 describesmorpholine-2,3-dione and its derivatives, as suitable postcrosslinkers.

The amount of postcrosslinker is preferably from 0.01 to 1% by weight,more preferably from 0.05 to 0.5% by weight, most preferably from 0.1 to0.2% by weight, based in each case on the polymer.

The postcrosslinking is typically performed in such a way that asolution of the postcrosslinker is sprayed onto the hydrogel or the drypolymer beads. The spraying is followed by thermal drying, and thepostcrosslinking reaction can take place either before or during thedrying.

The spraying of a solution of the crosslinker is preferably performed inmixers with moving mixing tools, such as screw mixers, paddle mixers,disk mixers, plowshare mixers and shovel mixers. Particular preferenceis given to vertical mixers, very particular preference to plowsharemixers and shovel mixers. Suitable mixers are, for example, Lödigemixers, Bepex mixers, Nauta mixers, Processall mixers and Schugi mixers.

The thermal drying is preferably carried out in contact dryers, morepreferably paddle dryers, most preferably disk dryers. Suitable dryersare, for example, Bepex dryers and Nara dryers. Moreover, it is alsopossible to use fluidized bed dryers.

The drying can be effected in the mixer itself, by heating the jacket orblowing in warm air. Equally suitable is a downstream dryer, for examplea staged dryer, a rotary tube oven or a heatable screw. It isparticularly advantageous to mix and dry in a fluidized bed dryer.

Preferred drying temperatures are in the range from 170 to 250° C.,preferably from 180 to 220° C. and more preferably from 190 to 210° C.The preferred residence time at this temperature in the reaction mixeror dryer is preferably at least 10 minutes, more preferably at least 20minutes, most preferably at least 30 minutes.

The process according to the invention enables the preparation ofwater-absorbing polymer beads with a high centrifuge retention capacity(CRC), a high absorbency under a load of 4.83 kPa (AUL0.7 psi), a highpermeability (SFC) and a low level of extractables.

The present invention further provides water-absorbing polymer beadswhich are obtainable by the process according to the invention.

The present invention further provides water-absorbing polymer beadswhich have a centrifuge retention capacity (CRC) of at least 30 g/g anda permeability (SFC) of at least 30×10⁻⁷ cm³s/g, and less than 30% ofthe measured moduli of elasticity of the outer bead surface have a valueof less than 60% of the mean modulus of elasticity.

The water-absorbing polymer beads obtainable by the process according tothe invention typically have the shape of hollow spheres. The presentinvention therefore further provides water-absorbing polymer beadscomprising at least one cavity in the bead interior.

The ratio of maximum diameter of the cavity to maximum diameter of thepolymer bead is preferably at least 0.1, more preferably at least 0.3,most preferably at least 0.4.

The quotient of mean modulus of elasticity of the outer bead surface andmean modulus of elasticity of the inner wall of the cavity is preferablyat least 2.5, more preferably at least 2.8, most preferably at least 3.

The inventive water-absorbing polymer beads are approximately round,i.e. the polymer beads have a mean sphericity of typically at least0.84, preferably at least 0.86, more preferably at least 0.88 and mostpreferably at least 0.9. The sphericity (SPHT) is defined as

${S\; P\; H\; T} = \frac{4\pi\; A}{U}$where A is the cross-sectional area and U is the cross-sectionalcircumference of the polymer beads. The mean sphericity is thevolume-average sphericity.

The mean sphericity can be determined, for example, with the Camsizer®image analysis system (Retsch Technolgy GmbH; Germany):

For the measurement, the product is introduced through a funnel andconveyed to the falling shaft with a metering channel. While the beadsfall past a light wall, they are recorded selectively by a camera. Theimages recorded are evaluated by the software in accordance with theparameters selected.

To characterize the roundness, the parameter designated as sphericity inthe program is employed. The parameters reported are the meanvolume-weighted sphericities, the volume of the beads being determinedvia the equivalent diameter xc_(min). To determine the equivalentdiameter xc_(min), the longest chord diameter for a total of 32different spatial directions is measured in each case. The equivalentdiameter xc_(min) is the shortest of these 32 chord diameters. Theequivalent diameter xc_(min) corresponds to the mesh size of a screenthat the bead can just pass through. To record the beads, the so-calledCCD-zoom camera (CAM-Z) is used. To control the metering channel, asurface coverage fraction of 0.5% is predefined.

Polymer beads with relatively low sphericity are obtained by reversesuspension polymerization when the polymer beads are agglomerated duringor after the polymerization.

The water-absorbing polymer beads prepared by customary solutionpolymerization (gel polymerization) are ground and classified afterdrying to obtain irregular polymer beads. The mean sphericity of thesepolymer beads is between approx. 0.72 and approx. 0.78.

The present invention further provides processes for preparing hygienearticles, especially diapers, comprising the use of water-absorbingpolymer beads prepared by the abovementioned process.

The present invention further provides for the use of inventivewater-absorbing polymer beads in hygiene articles, for thickeningwastes, especially medical wastes, or as a water-retaining agent inagriculture.

The water-absorbing polymer beads are tested by means of the testmethods described below.

Methods:

The measurements should, unless stated otherwise, be carried out at anambient temperature of 23±2° C. and a relative air humidity of 50±10%.The water-absorbing polymers are mixed thoroughly before themeasurement.

Saline Flow Conductivity (SFC)

The saline flow conductivity of a swollen gel layer under a load of 0.3psi (2070 Pa) is, as described in EP 640 330 A1, determined as the gellayer permeability of a swollen gel layer of water-absorbing polymerbeads, except that the apparatus described on page 19 and in FIG. 8 inthe aforementioned patent application was modified to the effect thatthe glass frit (40) is no longer used, the plunger (39) consists of thesame polymer material as the cylinder (37) and now comprises 21 bores ofequal size distributed uniformly over the entire contact surface. Theprocedure and evaluation of the measurement remain unchanged from EP 640330 A1. The flow rate is recorded automatically.

The saline flow conductivity (SFC) is calculated as follows:SFC [cm³s/g]=(Fg(t=0)×L0)/(d×A×WP),where Fg(t=0) is the flow rate of NaCl solution in g/s, which isobtained by means of a linear regression analysis of the Fg(t) data ofthe flow determinations by extrapolation to t=0. L0 is the thickness ofthe gel layer in cm, d is the density of the NaCl solution in g/cm³. Ais the surface area of the gel layer in cm², and WP is the hydrostaticpressure over the gel layer in dyn/cm².Mean Modulus of Elasticity

To determine the mean modulus of elasticity (Young's modulus ofelasticity), the water-absorbing polymer beads are swollen in excess0.9% by weight sodium chloride solution for 30 min. A glass micropipettehaving an internal diameter D of 50 μm is placed onto the bead surfaceto be examined. Subsequently, a reduced pressure is generated in themicropipette, such that the surface of the water-absorbing polymer beadto be examined is sucked into the micropipette. The length L is themaximum length by which the bead surface is sucked into themicropipette. The reduced pressure is selected such that the beadsurface sucked in has the shape of a meniscus and the length L isbetween 5 and 10 μm. The length L and the accompanying pressuredifference Δp measured relative to the surrounding solution in themicropipette are noted. Lengths L which are too small reduce theaccuracy of the measurement; at excess lengths L, the linear measurementrange is departed from, i.e. the length L is no longer proportional tothe pressure difference Δp. The fact that the linear range has beendeparted from can also be recognized in that the bead surface sucked inadjoins the inner wall of the micropipette.

The diameter of the swollen polymer beads should be at least 250 μm.When the bead diameters are too low, even the curvature of the polymerbead simulates a meniscus in the micropipette. To analyze smallerwater-absorbing polymer beads, it is therefore necessary to usemicropipettes having a smaller internal diameter, in which case therange for the length L should also be adjusted.

The mean modulus of elasticity is calculated according to

$E = {{\frac{3}{4\pi} \cdot \Delta}\;{p \cdot {\frac{D}{L}.}}}$

The measurement is repeated at least 20 times. The arithmetic mean ofthe values obtained is the mean modulus of elasticity.

The deformation of the water-absorbing polymer beads during themeasurment can be recorded by means of a digital imaging system andevaluated by computer.

FIG. 1 shows an example of a test setup on a microscope slide. In thisFIGURE, the reference numerals have the following meanings:

-   -   1 to image evaluation    -   2 to pressure measurement    -   3 to pressure generation    -   4 solution    -   5 polymer bead

When water-absorbing polymer beads which have the shape of hollowspheres are examined, it is also possible to measure the modulus ofelasticity of the inner wall of the cavity. To this end, the swollenwater-absorbing polymer beads are cut through by means of a scalpel.

Centrifuge Retention Capacity (CRC)

The centrifuge retention capacity of the water-absorbing polymer beadsis determined by the EDANA (European Disposables and NonwovensAssociation) recommended test method No. 441.2-02 “Centrifuge retentioncapacity”.

Absorbency Under Load (AUL0.7 psi)

The absorbency under load of the water-absorbing polymer beads isdetermined by the EDANA (European Disposables and Nonwovens Association)recommended test method No. 442.2-02 “Absorption under pressure”, usinga weight of 49 g/cm² (0.7 psi) instead of a weight of 21 g/cm² (0.3psi).

Extractables

The content of extractables of the water-absorbing polymer beads isdetermined by the EDANA (European Disposables and Nonwovens Association)recommended test method No 470.2-02 “Extractable”.

The EDANA test methods are obtainable, for example, from the EuropeanDisposables and Nonwovens Association, Avenue Eugene Plasky 157, B-1030Brussels, Belgium.

EXAMPLES Example 1 (Comparative Example)

14.3 kg of sodium acrylate (37.5% by weight solution in water), 1.4 kgof acrylic acid and 350 g of water were mixed with 22 g of 15-tuplyethoxylated trimethylolpropane triacrylate. The solution was dropletizedinto a heated dropletizer tower filled with a nitrogen atmosphere (180°C., height 12 m, width 2 m, gas velocity 0.1 m/s in cocurrent). Themetering rate was 16 kg/h. The dropletizer plate had 30×200 μm bores.Just upstream of the dropletizer, the initiator was metered into themonomer solution by means of a static mixer. The initiator used was a 3%by weight solution of2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride in water. Themetering rate of the initiator solution was 1.1 kg/h.

The water-absorbing polymer beads had the following properties:

CRC 34.5 g/g AUL0.7psi 16.2 g/g Extractables 4.0% by weight SFC 0.9 ×10⁻⁷ cm³s/g

The mean modulus of elasticity of the outer bead surface was 60 kPa, themean modulus of elasticity of the inner wall of the cavity was 30 kPaand the quotient of the mean moduli of elasticity was 2.

The mean modulus of elasticity is the mean value from 20 individualmeasurements. A total of 4 individual measurements of the modulus ofelasticity of the outer bead surface gave a value of less than 36 kPa.

The mean bead diameter was 350 μm.

Example 2 (Comparative Example)

The water-absorbing polymer beads from example 1 were sprayed with asolution of 0.08% by weight of ethylene glycol diglycidyl ether, 1.75%by weight of water and 1.17% by weight of propylene glycol, based ineach case on the water-absorbing polymer beads, and dried at 120° C. ina forced-air drying cabinet for 30 minutes.

The water-absorbing polymer beads had the following properties:

CRC 34.8 g/g AUL0.7psi 27.2 g/g Extractables 2.9% by weight SFC 16 ×10⁻⁷ cm³s/g

The mean modulus of elasticity of the outer bead surface was 150 kPa,the mean modulus of elasticity of the inner wall of the cavity was 40kPa and the quotient of the mean moduli of elasticity was 3.75.

The mean modulus of elasticity is the mean value from 20 individualmeasurements. A total of 10 individual measurements of the modulus ofelasticity of the outer bead surface gave a value of less than 90 kPa.

The mean bead diameter was 350 μm.

Example 3

14.3 kg of sodium acrylate (37.5% by weight solution in water), 1.4 kgof acrylic acid and 350 g of water were mixed with 22 g of 15-tuplyethoxylated trimethylolpropane triacrylate (first monomer solution).14.3 kg of sodium acrylate (37.5% by weight solution in water), 1.4 kgof acrylic acid and 350 g of water were mixed with 44 g of 15-tuplyethoxylated trimethylolpropane triacrylate (second monomer solution).The solutions were dropletized into a heated dropletizer tower filledwith nitrogen atmosphere (180° C., height 12 m, width 2 m, gas velocity0.1 m/s in cocurrent). The metering rate of the first monomer solutionwas 16 kg/h. The metering rate of the second monomer solution was 1.6kg/h. The dropletizer plate had 30×200 μm bores, and each bore wassurrounded by an annular gap. Just upstream of the dropletizer, theinitiator was metered into the monomer solutions by means of staticmixers. The initiator used was a 3% by weight solution of2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride in water. Themetering rate of the initiator solution into the first monomer solutionwas 1.1 kg/h. The metering rate of the initiator solution into thesecond monomer solution was 0.1 kg/h.

The water-absorbing polymer beads had the following properties:

CRC 34.5 g/g AUL0.7psi 22.1 g/g Extractables 3.5% by weight SFC 30 ×10⁻⁷ cm³s/g

The mean modulus of elasticity of the outer bead surface was 90 kPa, themean modulus of elasticity of the inner wall of the cavity was 40 kPaand the quotient of the mean moduli of elasticity was 2.25.

The mean modulus of elasticity is the mean value from 20 individualmeasurements. A total of 3 individual measurements of the modulus ofelasticity of the outer bead surface gave a value of less than 54 kPa.

The mean bead diameter was 360 μm.

Example 4

The procedure of example 3 was repeated. The second monomer solution wasprepared by using 88 g of 15-tuply ethoxylated trimethylolpropanetriacrylate.

The water-absorbing polymer beads had the following properties:

CRC 34.9 g/g AUL0.7psi 27.9 g/g Extractables 3.5% by weight SFC 50 ×10⁻⁷ cm³s/g

The mean modulus of elasticity of the outer bead surface was 140 kPa,the mean modulus of elasticity of the inner wall of the cavity was 50kPa and the quotient of the mean moduli of elasticity was 2.8.

The mean modulus of elasticity is the mean value from 20 individualmeasurements. A total of 4 individual measurements of the modulus ofelasticity of the outer bead surface gave a value of less than 84 kPa.

The mean bead diameter was 370 μm.

Example 5

The procedure of example 3 was repeated. The second monomer solution wasprepared by using 176 g of 15-tuply ethoxylated trimethylolpropanetriacrylate.

The water-absorbing polymer beads had the following properties:

CRC 34.0 g/g AUL0.7psi 29.3 g/g Extractables 3.0% by weight SFC 90 ×10⁻⁷ cm³s/g

The mean modulus of elasticity of the outer bead surface was 180 kPa,the mean modulus of elasticity of the inner wall of the cavity was 60kPa and the quotient of the mean moduli of elasticity was 3.

The mean modulus of elasticity is the mean value from 20 individualmeasurements. A total of 5 individual measurements of the modulus ofelasticity of the outer bead surface gave a value of less than 108 kPa.

The mean bead diameter was 380 μm.

Example 6 (Comparative Example)

The procedure of example 6 of WO 2006/077054 A1 was repeated.

The water-absorbing polymer beads had the following properties:

CRC 21.2 g/g AUL0.3psi 17.6 g/g Extractables 17.5% by weight SFC 12 ×10⁻⁷ cm³s/g

The mean modulus of elasticity of the outer bead surface was 80 kPa, themean modulus of elasticity of the inner wall of the cavity was 40 kPaand the quotient of the mean moduli of elasticity was 2.

The mean modulus of elasticity is the mean value from 20 individualmeasurements. A total of 4 individual measurements of the modulus ofelasticity of the outer bead surface gave a value of less than 48 kPa.

The mean bead diameter was 210 μm.

Example 7 (Comparative Example)

14.275 kg of sodium acrylate (37.5% by weight solution in water) and1.367 kg of acrylic acid were mixed with 0.358 kg of water, 22 g of15-tuply ethoxylated trimethylolpropane triacrylate and 80 g of EDTA(10% by weight solution of the sodium salt of ethylenediaminetetraaceticacid in water). After addition of 33 g of2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (3% by weightsolution in water) and 110 g of hydrogen peroxide (3% by weight solutionin water), the solution was dropletized into a heated dropletizationtower filled with nitrogen atmosphere (180° C., height 12 m, width 2 m,gas velocity 0.1 m/s in cocurrent). The metering rate was 16 kg/h. Thedropletizer plate had 37×170 μm bores. The diameter of the dropletizerplate was 65 mm. Just upstream of the dropletizer, the initiator wasmixed with the monomer solution by means of a static mixer.

The water-absorbing polymer beads had the following properties:

CRC 33.0 g/g AUL0.7psi 25.0 g/g Extractables 7.0% by weight SFC 10 ×10⁻⁷ cm³s/g

The mean modulus of elasticity of the outer bead surface was 90 kPa, themean modulus of elasticity of the inner wall of the cavity was 40 kPaand the quotient of the mean moduli of elasticity was 2.25.

The mean modulus of elasticity is the mean value from 20 individualmeasurements. A total of 3 individual measurements of the modulus ofelasticity of the outer bead surface gave a value of less than 54 kPa.

The mean bead diameter was 360 μm.

The invention claimed is:
 1. Water-absorbing polymer beads which have acentrifuge retention capacity of at least 30 g/g and a permeability ofat least 30×10⁻⁷ cm³s/g, and less than 30% of a measured moduli ofelasticity of an outer bead surface has a value of less than 60% of themean modulus of elasticity, wherein the polymer beads have acrosslinking gradient and comprise at least one cavity in the beadinterior.
 2. The polymer beads according to claim 1, which have anabsorbency under a load of 4.83 kPa (AUL0.7psi) of at least 20 g/g. 3.The polymer beads according to claim 1, wherein the outer bead surfaceof the polymer beads has a mean modulus of elasticity of at least 100kPa.
 4. The polymer beads according to claim 1, which comprise less than10% by weight of extractables.
 5. The polymer beads according to claim1, wherein a ratio of maximum diameter of the cavity to a maximumdiameter of the polymer bead is at least 0.1.
 6. The polymer beadsaccording to claim 1, wherein a quotient of mean modulus of elasticityof an outer bead surface and mean modulus of elasticity of an inner wallof the cavity is at least 2.5.
 7. The polymer beads according to claim1, which comprise at least partly neutralized polymerized acrylic acidto an extent of at least 50 mol %.
 8. The polymer beads according toclaim 1, which have a mean diameter of at least 200 μm.
 9. A hygienearticle comprising the polymer beads according to claim 1.